Organic Compounds

ABSTRACT

5,9-dimethyl-9-hydroxy-decen-4-al, having the formula (I)

This is an application filed under 35 USC 371 of PCT/EP2014/062002,which in turn claims priority to EP 13290129.9 filed 10 Jun. 2013, theentire contents of which are herein incorporated by reference.

This invention relates to a novel compound, a method of preparing thecompound, and its use as a fragrance ingredient, in particular its useas a fragrance ingredient to impart a muguet odour characteristic to aperfume composition. The invention also relates to perfume compositionsand to articles, such as fine fragrances or consumer productcompositions perfumed by the compound, or the perfume compositionscontaining said compound.

Compounds having muguet (or lily of the valley) odour characteristicsare very sought after as perfume ingredients. These compounds areimportant ingredients in floral bases and can act as harmonizers acrossmany types of fragrance creations. Compounds of this type are usedwidely in personal care and consumer care products, as well as in fineperfumery, to generate pleasant odours or to mask unpleasant odours.

An excellent perfume ingredient widely valued for its muguet odour noteis 4(4-hydroxy-4-methylpentyl) 3-cyclohexene carboxaldehyde, otherwiseknown as cyclohexal (Lyral™) This compound has found wide use in fineperfumery as well as in personal and household care products. Howeveraccording to findings of the European Scientific Committee for ConsumerSafety (SCCS) it has allergenic concerns and at the present time may besubject to regulatory action in the EU.

The problem addressed by the present invention is to provide newingredients and new perfume preparations, in particular, which areperceived and recognised by perfumers as having substantially the sameodour characteristics as cyclohexal, as well as having similar or evenimproved perfume performance compared to cyclohexal.

Accordingly, the invention provides in a first aspect the compound5,9-dimethyl-9-hydroxy-decen-4-al, having the formula (I)

The compound according to the present invention was found by theapplicant to have a classic floral, green muguet odour note that wasreminiscent of cyclohexal. Accordingly,5,9-dimethyl-9-hydroxy-decen-4-al could be an eminently suitablereplacement for cyclohexal.

A process of preparing γ,δ-unsaturated aldehydes and ketones isdisclosed in GB 981,702. This patent generally describes the reaction ofallylic alcohols with enol ethers, followed by a rearrangement reactionat elevated temperature. In an attempt to demonstrate the scope of thesynthetic procedure, examples are provided using a variety of allylicalcohols bearing different functionality. The examples include allylicalcohols bearing saturated and unsaturated alkyl groups, cycloalkanes,double bonds, aromatic rings, as well as oxygen containingfunctionality, such as hydroxyl groups.

In Example 27 of GB 981,702, it purports to describe a method ofpreparing the compound 5,9-dimethyl-9-hydroxy-decen-4-al starting fromthe hydroxyl-substituted allylic alcohol substrate, hydroxylinalool.

The reaction proceeds by mixing hydroxy linalool with vinyl ethyl etherin phosphoric acid. This organic mixture is worked-up in base anddistilled, before the distillate is added to an aqueous solution ofsodium bisulphite and the organic layer is discarded. The aqueous phaseis then treated with 30% sodium hydroxide before being extracted withether. The aqueous layer is discarded and the ethereal layer is treatedwith bicarbonate. After evaporation of the ether, the crude product isdistilled to isolate the final product. The final product wascharacterised by its odour characteristics, as well as its boiling pointand refractive index.

The isolated final product was described as having a “pleasantly fruityand smoky-fatty odour”. This finding was curious in view of theapplicant's own finding that the target compound5,9-dimethyl-9-hydroxy-decen-4-al actually exhibits a classical muguetodour, which is completely unrelated to the odour reported in GB981,702. Furthermore, the boiling point and refractive indexmeasurements of the compound 5,9-dimethyl-9-hydroxy-decen-4-al, asmeasured by the applicant, differs markedly from the product obtainedaccording to the process of this Example 27. Specifically, the productobtained in Example 27 had a reported boiling point of 83-85° C./0.03 mmand a refractive index n_(D) ²⁰ of 1.4698. In fact, the true values for5,9-dimethyl-9-hydroxy-decen-4-al were found by the applicant to be106-109° C./0.05 mm, and n_(D) ²⁰ of 1.4659.

When the applicant reproduced the synthetic conditions described inExample 27 it was not possible to recover any5,9-dimethyl-9-hydroxy-decen-4-al. In fact, what was recovered, afterremoving a large amount of polymeric residue was an isomeric mixture ofthe compound:

Upon analysis, this compound was found to have a boiling point of 85° C.at 0.03 mm and an N_(D) ²⁰ of 1.4682. Furthermore, the odourcharacteristics were described by perfumers to be fruity, citrus, fatty,slightly hot iron and metallic. Conspicuously, these parameters showedremarkable conformance with those disclosed for the isolated finalproduct of GB 981,702, Example 27.

From the foregoing, it is quite apparent that GB 981,702 does notconstitute an enabling disclosure regarding the compound5,9-dimethyl-9-hydroxy-decen-4-al, or its preparation. Indeed, what theauthors of GB 981,702 did not appreciate, and what the applicant hasfound after considerable research effort into this reaction, is that theintroduction of a hydroxyl substituent in the allylic alcohol startingmaterial (as in the case of hydroxylinalool of Example 27, which is theonly example of the use of a hydroxyl-substituted allylic alcoholstarting material), greatly changes the stability and chemicalproperties of the product. The use of sulphite adducts as a means ofseparating aldehydes from complex mixtures is a known technique used bythe authors of GB981,702, however, liberation of the final product fromthe adduct is achieved by hydrolysis in strong base (30% sodiumhydroxide), as well as subsequent treatment with strong acid and thiscauses undesirable side reactions.

Applicant surprisingly discovered that 5,9-dimethyl-9-hydroxy-decen-4-alis both thermally unstable, and unstable in alkaline media, thereforegentle reaction and isolation conditions are required if it is to besuccessfully prepared.

Accordingly, in another aspect of the present invention there isprovided a method of preparing 5,9-dimethyl-9-hydroxy-decen-4-al (I)from a reaction mixture, comprising the step of presenting the reactionmixture in a form substantially free of any acid or base, and distillingthe mixture 5,9-dimethyl-9-hydroxy-decen-4-al from the reaction mixture.

In a particular embodiment of the present invention the reaction mixturemay be presented in a form substantially free of acid or base if it isneutralised with an aqueous washing liquour, which may be one or more ofwater, optionally containing a salt, such as sodium chloride, an aqueoussolution of an acid or an aqueous solution of a base.

The acid may be selected from the group consisting of C-1 to C4carboxylic acids, such as acetic acid, polycarboxylic acids such ascitric acid and weak mineral acids.

The base may be selected from the group consisting of a weak base, suchas sodium or potassium (hydrogen) carbonate.

The reaction mixture is deemed to be substantially free of acid or basewhen after washing, the washing liquour has a pH of between about 6.5 toabout 7.5.

The applicant found that in alkaline conditions above pH 10, or inacidic conditions below about pH 4,5,9-dimethyl-9-hydroxy-decen-4-al israpidly degraded at ambient temperature, and the degradation proceedseven more rapidly at elevated temperatures. Accordingly, if the objectof preparing and isolating 5,9-dimethyl-9-hydroxy-decen-4-al is to beachieved, it should not be subjected to alkaline conditions, of ifalkaline conditions are encountered, they should not be above 10, moreparticularly above 9.5, and still more particularly above 9. Strongbases, such as sodium hydroxide should be avoided, preferably, althoughif used, care should be taken that the pH does not rise to theaforementioned values. And furthermore, when distilling5,9-dimethyl-9-hydroxy-decen-4-al in order to present it in olfactivelypure form, it should be first ensured that the reaction mixturecontaining it is substantially free of acid or base, as stated hereinabove.

Distillation may be carried out at a temperature of 95° C. to 200° C.and at a pressure of 0.01 mm to 10 mm, more particularly 0.01 mm to 5mm.

Due to the thermal sensitivity of 5,9-dimethyl-9-hydroxy-decen-4-al, itmay be desirable if the distillation step is shortened in duration asmuch as possible. In order to simplify the distillation process and toshorten the duration, one can first separate5,9-dimethyl-9-hydroxy-decen-4-al from organic by-products of thereaction mixture by treating 5,9-dimethyl-9-hydroxy-decen-4-al withaqueous sodium metabisulphite to form the sulphonate of5,9-dimethyl-9-hydroxy-decen-4-al, which is soluble in the aqueousphase. The sulphonate of the following formula forms another aspect ofthe present invention.

Thereafter, an organic solvent, can be added to the aqueous phase and5,9-dimethyl-9-hydroxy-decen-4-al can be regenerated by treating thesulphonate with a dilute solution of a weak base, for example sodiumcarbonate. Once regenerated, 5,9-dimethyl-9-hydroxy-decen-4-alpartitions into the organic phase, and this phase is washed with diluteweak acid to remove traces of base, before distillation is undertaken.

5,9-dimethyl-9-hydroxy-decen-4-al may be prepared from an allylicalcohol precursor. This precursor may be linalool, or ahydroxyl-substituted allylic alcohol, such as hydroxylinalool. Stillfurther, it could be a hydroxyl-substituted allylic alcohol, wherein thenon-allylic hydroxyl substituent is in a protected or masked form, suchas its acetate.

The allylic alcohol precursor is converted to5,9-dimethyl-9-hydroxy-decen-4-al by carrying out a ClaisenRearrangement reaction in the presence of an acid, which is a techniquewell known to a skilled person in the art. The acid is employed to firsteffect a trans-etherification on the allylic hydroxyl group, and it isthe ether that is formed, which undergoes the rearrangement reaction, asis well known in the art.

The allylic alcohol precursor has the following formula:

wherein,

is a double bond or a single bond, and

is a hydroxyl group or a protected hydroxyl group, such as an acetate,silyl ether or mixed acetal, provided that

is present only when

is a single bond.

In a preferred embodiment of the present invention, the precursor ishydroxy linalool, however, a protected form of hydroxy linalool, e.g.the acetate, might also be employed.

If the precursor contains the group

as a double bond, once the Claisen Rearrangement is carried out, thatdouble bond can be hydrolysed to add a hydroxyl group and release thedesired 5,9-dimethyl-9-hydroxy-decen-4-al, according to techniques knownto a person skilled in the art. Thereafter, steps are taken to ensurethe reaction mixture contains substantially no acid or base before beingsubjected to distillation, as described hereinabove.

The allylic alcohol precursors are either commercially available, or canbe prepared from commonly available starting materials using techniquesknown to the person skilled in the art.

The Claisen Rearrangement reaction occurs readily when a vinyl ether isreacted with an allylic alcohol precursor, in the presence of an acid ormetal catalyst, at a temperature in a range spanning ambient to about200° C. Typically, the reaction is carried out at high pressure in anautoclave. Any desired pressure above atmospheric can be employed in anautoclave, for example, up to 100 bar, and more particularly about 5 to20 bar.

The applicant has found, however, that the reaction can be carried outat atmospheric pressure, in an unpressurised reaction vessel, whenemploying diethyleneglycol divinylether or triethyleneglycol divinylether, as the vinyl ether.

Optionally, the reaction is carried out under an inert atmosphere, forexample under a nitrogen atmosphere.

Once the rearrangement reaction is complete, the reaction mixture can betreated with acid to hydrolyze any acetals that are formed during thecourse of the reaction.

In a particular embodiment of the present invention there is provided amethod of preparing 5,9-dimethyl-9-hydroxy-decen-4-al (I), comprisingthe steps of reacting an allylic alcohol precursor, preferably hydroxylinalool, with diethyleneglycol divinylether in the presence of an acidunder an inert gas atmosphere, at atmospheric pressure and a temperatureof 125 to 200° C.; treating the reaction mixture containing5,9-dimethyl-9-hydroxy-decen-4-al with dilute acid to hydrolysesubstantially all acetals; and remove substantially all acids and bases,before subjecting the neutralised reaction mixture to distillation in amanner described above.

In another aspect of the present invention there is provided a method ofpreparing 5,9-dimethyl-9-hydroxy-decen-4-al (I), said method comprisingthe steps of:

-   -   I) reacting hydroxylinalool (3) with ethyl vinyl ether in acid        under an inert gas atmosphere at 1 to 100 bar, more specifically        at 5-20 bar and a temperature of −10 to 200 degrees centigrade,        more specifically at 140-190 degrees centigrade to form a        reaction mixture comprising acetals;    -   II) acidifying the cooled reaction mixture at −20 to 40 degrees        centigrade and atmospheric pressure to hydrolyse said acetals;    -   III) neutralising the reaction mixture in a base before        adjusting the pH of the reaction mixture to a slightly acidic pH        of 4 to 6, to yield 5,9-dimethyl-9-hydroxy-decen-4-al (I); and    -   IV) distilling the reaction mixture to isolate pure        5,9-dimethyl-9-hydroxy-decen-4-al (I).

The rearrangement reaction described above, for example, the reaction ofhydroxylinalool (3) with ethyl vinyl ether described above, proceedsunder acidic conditions. Particular acids useful in the presentinvention include phenyl phosphonic acid, sulfosalicylic acid,phosphoric acid buffered with various amounts of amines, phosphoricacid, ammonium salts, alkyl carboxylic acids and aryl carboxylic acids.

Whereas hydroxylinalool (3) is a commonly available starting material,it can be formed in a straightforward manner starting from3,7-dimethyloct-6-en-1-yn-3-ol (1) and hydrating this compound inaqueous sulphuric acid to afford the compound (2). Selectivehydrogenation of the triple bond with a suitable catalyst, such as apalladium catalyst leads to hydroxyl linalool (3), which can be furtherconverted to the target compound 5,9-dimethyl-9-hydroxy-decen-4-al (I)in accordance with the preparative method of the present invention. Ageneral reaction scheme is set forth Scheme 1.

5,9-dimethyl-9-hydroxy-decen-4-al (I) can be provided in pure orenriched form in respect of its E- or Z-isomers. The strength (i.e.detection threshold) as well as the olfactive character or quality ofthis odourant may be affected by the relative proportions of geometricisomers contained in isomeric mixtures. If pure forms of the isomers aredesired they can be obtained using synthetic procedures or by physicalseparation as is generally known in the art.

In a particular embodiment of the invention the E/Z ratio of5,9-dimethyl-9-hydroxy-decen-4-al (I) is within the range of 8:2 to 2:8,or more particularly in a ratio of 6:4.

In a particular embodiment of the invention, a particularly desirableolfactive impression is obtained when 50 to 70 wt % of5,9-dimethyl-9-hydroxy-decen-4-al is present in the E-form, and 30 to 50wt % is in the Z-form.

The compound of formula (I) can be purified to afford its olfactivelypure form, that is, a form in which there are no traces of impuritypresent at levels that can substantially affect odour character orquality. The applicant has found, however, that certain by-products fromthe reaction mixture from which 5,9-dimethyl-9-hydroxy-decen-4-al isisolated can complement the odour quality, or not adversely affect theodour quality, at least.

Accordingly, in another aspect of the invention there is provided aperfume mixture comprising 5,9-dimethyl-9-hydroxy-decen-4-al (I) and acompound according to the formula (II)

In a particular embodiment of the present invention there is provided aperfume mixture comprising 5,9-dimethyl-9-hydroxy-decen-4-al (I) and acompound according to the formula (II) in a ratio (weight/weight) thatis 95 to 5 parts; more particularly 99 to 1 part, more particularly 99.1to 0.9 parts; 99.2 to 0.8 parts; 99.3 to 0.7 parts; 99.4 to 0.6 parts;99.5 to 0.5 parts; 99.6 to 0.4 parts; 99.7 to 0.3 parts; 99.8 to 0.2parts; 99.9 to 0.1 parts; 99.95 to 0.05 parts; or 99.99 to 0.01 parts.The skilled person will appreciate that the compound of formula (II) mayexist in pure form or may exist as a mixture of isomers. Theaforementioned ratios relate to both the compound (II) in isomericallypure form or in any isomeric mixture thereof.

The compound of formula (I) and perfume mixtures referred to hereinabovewere found to exhibit odour characteristics that are similar tocyclohexal, and as such can be employed in perfume compositions as areplacement for cyclohexal.

Accordingly, in another aspect of the present invention there isprovided the use of a compound of formula (I), alone or in admixturewith a compound (II) as a replacement for cyclohexal.

In yet another aspect of the present invention there is provided aperfume composition comprising a compound of formula (I) alone or inadmixture with a compound of formula (II), and which is free ofcyclohexal.

In yet another aspect of the present invention there is providedperfumed article, such as a fine fragrance or a personal or householdcare product, perfumed with a a compound of formula (I), optionally inadmixture with a compound of formula (II).

Whereas the compound of formula (I) or the mixtures referred to abovehave very similar odour characteristics as cyclohexal, nevertheless aperfumer may find it desirable to employ additional perfume ingredientsin combination with the compound of formula (I) or the perfume mixtures,in order to balance or fine tune the odour characteristics, for example,to bring the compound or mixtures referred to above into even closerconformance with the odour characteristics of cyclohexal.

Accordingly, in another aspect of the present invention there isprovided a perfume composition comprising a compound according toformula (I), optionally in admixture with a compound of formula (II) ashereinabove described, together with one or more of the followingingredients: 2-cyclohexylidene-2-phenylacetonitrile, e.g. PEONILE™;4-(octahydro-4,7-methano-5H-inden-5-ylidene)butanal, e.g. DUPICAL™; and4-methyl-2-(2-methylpropyl)tetrahydro-2H-pyran-4-ol, e.g. FLOROSA™;methyl 2-(2-hexyl-3-oxocyclopentyl)acetate, e. g. HEDIONE™.

In a particular embodiment of the present invention a perfumecomposition comprises 2-cyclohexylidene-2-phenylacetonitrile.

In another particular embodiment of the invention, a perfume compositioncomprises 2-cyclohexylidene-2-phenylacetonitrile and4-methyl-2-(2-methylpropyl)tetrahydro-2H-pyran-4-ol.

In yet another particular embodiment of the invention, a perfumecomposition comprises 2-cyclohexylidene-2-phenylacetonitrile and4-Methyl-2-(2-methylpropyl)tetrahydro-2H-pyran-4-ol and4-(octahydro-4,7-methano-5H-inden-5-ylidene)butanal.

In a perfume composition according to the present invention2-cyclohexylidene-2-phenylacetonitrile, e.g. PEONILE™ may be employed in0.001 to 10 parts by weight per 1 part by weight5,9-dimethyl-9-hydroxy-decen-4-al.

In a perfume composition according to the present invention4-methyl-2-(2-methylpropyl)tetrahydro-2H-pyran-4-ol, e.g. FLOROSA™ maybe employed in 0.01 to 20 parts by weight per 1 part by weight5,9-dimethyl-9-hydroxy-decen-4-al.

In a perfume composition according to the present invention4-(octahydro-4,7-methano-5H-inden-5-ylidene)butanal, e.g. DUPICAL™ maybe employed in 0.0001 to 0.5 parts by weight per 1 part by weight5,9-dimethyl-9-hydroxy-decen-4-al.

In a perfume composition according to the present invention methyl2-(2-hexyl-3-oxocyclopentyl)acetate, e. g. HEDIONE™ may be employed in0.001 to 10 parts by weight per 1 part by weight5,9-dimethyl-9-hydroxy-decen-4-al.

In a perfume composition, the compound of formula (I), optionally incombination with a compound (II) may be employed in an amount of about 1to 30%, more particularly 5-20%, by weight based on the total weight ofsaid perfume composition.

The perfume compositions described above, exhibit the odourcharacteristics of cyclohexal, but the perfume compositions need not belimited only to these ingredients. The perfume compositions may containone or more additional fragrance ingredients.

Particular perfume ingredients that may be used harmoniously with thecompound of the formula (I) include:

Natural ingredients, such as those selected from Iris, Mimosa, Ylang,Bergamot, jasmine and rose;

Synthetic muguet fragrance ingredients such as Cyclamen aldehyde(103-95-7), Hydroxycitronellal (107-75-5), Hydroxy Citronellal diethylacetal (7779-94-4), Lilial (80-54-6), Cyclohexal (31906-04-4), Silvial(6658-48-6), Bourgeonal (18127-01-0), Florhydral (125109-85-5), andCyclemax (7775-00-0);

Harmonic floral ingredients of the rose type such as ethyl phenylalcohol (60-12-8), Dimethyl phenyl ethyl carbinol (103-05-9),Citronellol (106-22-9), Rhodinol (106-22-9), Acet. DMBC (151-05-3),Geraniol (106-24-1), Nerol (106-25-2), Nerolidol (7212-44-4), Mefrosol(55066-48-3), Peomosa (19819-98-8), citronellyl iso butyrate (97-89-2),and Majantol (103694-68-4);

Harmonic floral ingredients of the freesia type such as Linalool(78-70-6), Rossitol (215231-33-7), and Coranol (83926-73-2);

Harmonic floral ingredients of the lilac type such as Alc. Cinnamicalcohol (104-54-1), propyl phenyl alcohol (122-97-4) and Terpineol(8000-41-7);

Harmonic floral ingredients of the jasmine type such as benzyl acetate(140-11-4), Hedione (24851-98-7), Hexyl Cinnamic aldehyde (101-86-0),and Amyl Cinnamic aldehyde (122-40-7);

Harmonic floral ingredients of the muguet type such as Super Muguet(26330-65-4), Hydroxycitronellal dimethyl acetate (141-92-4), Magnol(92046-49-6), Mugetanol (63767-86-2), Mugesia (56836-93-2), Indole(120-72-9), and Indolene (67860-00-8);

Green harmonic ingredients such as cis 3 Hexenol (928-96-1), phenylacetic aldehyde (122-78-1), Maceal (67845-30-1), cis 3 hexenyl acetate(3681-71-8), Acetal CD (29895-73-6), Precarone (74499-58-4), Mefranal(55066-49-4), Elintaal (40910-49-4), Glycolierral (68901-32-6), andCoranol (83926-73-2);

Fresh harmonic ingredients such as C11 undecelenic aldehyde (112-45-8),C11 undecylic aldehyde (112-44-7), C10 aldehyde (112-31-2), C12 MNAaldehyde (110-41-8), Tropional (1205-17-0), Citral (5392-40-5), Oxyde deLimette (73018-51-6), Florhydral (125109-85-5), Floralozone(67634-15-5), Dihydro Farnesal (51513-58-7), Dihydrofarnesol(51411-24-6), Adoxal (141-13-9), Citronellyl Oxyacetaldehyde(7492-67-3), Floral super (71077-31-1) and Dodecenal (4826-62-4);

Harmonic woody ingredients such as Irisone (8013-90-9) and methyl Ionone(1335-46-2);

Harmonic powdery ingredients such as Fixolide (21145-77-7), Thibetolide(106-02-5), Heliotropine (120-57-0) and Vanilline (121-33-5); and

Diverse harmonic floral ingredients such as Phixia (107-75-5), Farnesal(19317-11-4), Farnesyle acetate (29548-30-9), Rhodinyl acetate(141-11-7), Cyclomethylene Citronellol (15760-18-6), Mayol (5502-75-0),Myraldyl acetate (72403-67-9), and Melonia (3613-30-7), wherein the CASnumbers of the molecules are provided in parentheses.

In addition to the aforementioned perfume ingredients that may beemployed as being particularly complimentary to the odourcharacteristics of the compound of formula (I), other fragranceingredients commonly used in perfumery may be employed, for example anyof those ingredients described in “Perfume and Flavour Chemicals”, S.Arctander, Allured Publishing Corporation, 1994, IL, USA, which isincorporated herein by reference, including essential oils, plantextracts, absolutes, resinoids, odourants obtained from natural productsand the like. However, it is preferred that the perfume compositionscontain no, or substantially no, cyclohexal.

Furthermore, perfume compositions may comprise adjuvants that arecommonly employed in perfumery. The term “adjuvant” refers toingredients, which are employed in perfume compositions for reasonsother than, or not specifically related to, a composition's odourcharacteristics. For example, an adjuvant may be an ingredient that actsas an aid to processing a perfume ingredient or ingredients, or acomposition containing said ingredient(s), or it may improve handling orstorage of a perfume ingredient or composition containing same. It mightalso be an ingredient that provides additional benefits such asimparting colour or texture. It might also be an ingredient that impartslight resistance or chemical stability to one or more ingredientscontained in a perfume ingredient or mixture or composition containingsame. A detailed description of the nature and type of adjuvants thatcan be employed in perfume mixtures or compositions containing samecannot be exhaustive, but it has to be mentioned that said ingredientsare well known to a person skilled in the art. Examples of adjuvantsinclude solvents and co-solvents; surfactants and emulsifiers; viscosityand rheology modifiers; thickening and gelling agents; preservativematerials; pigments, dyestuffs and colouring matters; extenders, fillersand reinforcing agents; stabilisers against the detrimental effects ofheat and light, bulking agents, acidulants, buffering agents andantioxidants.

In a particular embodiment of the present invention a compositioncomprising a compound of formula (I), optionally in combination with acompound of formula (II) or perfume composition containing same, asherein defined, contains an anti-oxidant adjuvant. Said anti-oxidant maybe selected from Tinogard® TT (BASF), Tinogard® Q (BASF), Tocopherol(including its isomers, CAS 59-02-9; 364-49-8; 18920-62-2; 121854-78-2),2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT, CAS 128-37-0) andrelated phenols, hydroquinones (CAS 121-31-9). More specifically,Tinogard Q in triethyl citrate (TEC) can be preferentially used as anantioxidant of 5,9-dimethyl-9-hydroxy-decen-4-al. The antioxidants maybe applied in levels of 0.5 to 3% in the neat compound5,9-dimethyl-9-hydroxy-decen-4-al.

As stated hereinabove, certain levels of compound (II) can be employedto compliment the odour characteristics of5,9-dimethyl-9-hydroxy-decen-4-al (I). However, for reasons related toolfactive quality, the levels of compound (II) should not be too high,and preferably should not extend beyond the levels referred tohereinabove. Applicant found that unless precautions are taken toprevent excessive oxidation of 5,9-dimethyl-9-hydroxy-decen-4-al (I),undesirable levels of compound (II) can be produced. Accordingly, ananti-oxidant should be employed in combination with5,9-dimethyl-9-hydroxy-decen-4-al (I).

Any one or more of the perfume ingredients or adjuvants employed in thepresent invention might be formulated in a delivery vehicle if desiredto provide a desired effect. Delivery vehicles may include encapsulates.Alternatively, a delivery vehicle may be in the form of a solid support,e.g. a polymeric support material onto which one or more perfumeingredients or adjuvants may be chemically or physically bound. Stillfurther, one or more perfume ingredients or adjuvants may be dissolvedor dispersed in a matrix material, which serves to control the rate atwhich said ingredient or ingredients emanates therefrom. In yet analternative embodiment, one or more ingredients or adjuvants may besupported on a porous substrate, such as a cyclodextrin or a zeolite orother inorganic material. In a still further embodiment, one or moreperfume ingredients may be provided in the form of a pro-perfume, whichwill react in a suitable environment to release the perfume ingredientin a controlled manner.

Having regard to the foregoing, it will be appreciated that a perfumemixture or a perfume composition may be fragrance is at least partly insolid form, in gel form, in foam form and/or liquid form. If it ispresent in solid form, it then it may take the form of granules, powdersor tablets.

The compound of formula (I), perfume mixtures or perfume compositionsdescribed herein may be employed to add a characteristic odour to allmanner of articles, such as fine fragrances, personal care and householdcare compositions.

According to another aspect of the present invention there is provided amethod of imparting a muguet odour to a composition comprising the stepof adding to said composition a compound according to formula (I), aperfume mixture or a perfume composition containing said compound.

Personal and household care compositions include, but are not limited toa textile treatment product, an ironing aid, a cleaning cloth, a laundrydetergent, a cleaning product, in particular, for hard and/or softsurfaces, a household cleaner, a care product, a wash care product, alaundry care product, a room fragrancer, and air freshener, aconditioner, a colorant, a fabric conditioner, a conditioning substrate,a pharmaceutical, a crop protection product, a polish, a food, acosmetic product, a fertilizer, a building material, an adhesive, ableach, a decalcifier, an autocare product, floorcare product,cookercare product, leathercare product or furniture care product, ascourer, a disinfectant, a fragrancer, a mold remover and/or a precursorof the aforementioned products.

The skilled person is fully aware of the applicability of perfumeingredients, mixtures and compositions to personal and house hold carecompositions and a very detailed description of such compositions is notwarranted here. However, specific compositions that can be mentionedinclude cleaning compositions; autocare compositions; Cosmeticcompositions; textile treatment compositions; and Air freshener and aircare compositions.

Cleaning products include:

Toilet cleaners or lavatory cleaners, in other words, products forcleaning lavatory bowls and urinals, these products being suppliedpreferably in the form of powders, blocks, tablets or liquids,preferably gels. Besides other typical ingredients such as surfactants,they generally include organic acids e.g., citric acid and/or lacticacid) or sodium hydrogen sulfate, amidosulfuric acid or phosphoric acidfor removing limescale or urine scale;

Pipe-cleaning products or drain cleaners. These are typically stronglyalkaline products which serve in general to remove pipe blockagescomprising organic materials-such as hair, fat, food residues, soapdeposits, and the like. Additions of Al powder or Zn powder may servefor the formation of H2 gas with an effervescence effect. Possibleingredients are commonly alkalis, alkaline salts, oxidizing agents, andneutral salts. Supply forms in powder form preferably also includesodium nitrate and sodium chloride. Pipe-cleaning products in liquidform may preferably also include hypochlorite. There are alsoenzyme-based drain cleaners as well. Acidic products are likewisepossible;

Universal or all-purpose or general-purpose cleaners. These are cleanerswhich can be used universally for all hard surfaces in the household andin commerce that can be wiped down wet or damp. Generally speaking, theyare neutral or slightly alkaline or slightly acidic products, especiallyliquid products. All-purpose or general-purpose cleaners generallycontain surfactants, builders, solvents and hydrotropes, dyes,preservatives, and the like;

All-purpose cleaners with special disinfectant properties. Theyadditionally include active antimicrobial ingredients (e.g., aldehydes,alcohols, quaternary ammonium compounds, amphoteric surfactants,triclosan);

Sanitary cleaners. These are products for cleaning in bath and toilet.The alkaline sanitary cleaners are used preferably for removing fattysoiling, whereas the acidic sanitary cleaners are employed inparticular, for removing limescale. Sanitary cleaners advantageouslyalso have a considerable disinfectant action, particularly the stronglyalkaline sanitary cleaners that contain chlorine;

Oven cleaners or grill cleaners which may be supplied in the form ofgels or foam sprays. They generally serve for removing burnt-on orcarbonized food residues. Oven cleaners are preferably given a stronglyalkaline formulation using, for example, sodium hydroxide, sodiummetasilicate, 2-aminoethanol. In addition they generally contain anionicand/or nonionic surfactants, water-soluble solvents, and, in some cases,thickeners such as polycarboxylates and carboxymethylcellulose;

Metal polishes. These are cleaners for particular types of metal such asstainless steel or silver. Stainless steel cleaners preferably contain,besides acids (preferably up to 3% by weight, e.g., citric acid, lacticacid), surfactants (in particular, up to 5% by weight, preferablynonionic and/or anionic surfactants), and water, solvents as well(preferably up to 15% by weight) to remove fatty soiling, and alsofurther compounds such as thickeners and preservatives. Very finepolishing structures are included, furthermore, in products forpreferably bright stainless steel surfaces. Silver polishes, in turn,may be provided in an acidic formulation. In particular, for removingblack deposits of silver sulfide they contain, preferably, complexingagents (e.g., thiourea, sodium thiosulfate). Typical supply forms arepolishing cloths, dipping baths, pastes, and liquids. Darkdiscolorations (oxide layers) are removed using copper cleaners andnonferrous-metal cleaners (e.g., for brass and bronze). They generallyhave a weakly alkaline formulation (preferably with ammonia) and ingeneral contain polishing agents and also, preferably, ammonium soapsand/or complexing agents;

Glass cleaners and window cleaners. These products serve preferably toremove dirt, especially greasy dirt, from glass surfaces. Preferablythey contain compounds such as anionic and/or nonionic surfactants (inparticular, up to 5% by weight), ammonia and/or ethanolamine (inparticular, up to 1% by weight), ethanol and/or 2-propanol, glycolethers (in particular, 10-30% by weight), water, preservatives, dyes,anti-misting agents and the like; and

Special-purpose cleaning products, examples being those forglass-ceramic hobs, and also carpet cleaners and stain removers.

Autocare products include:

Paint preservers, paint polishes, paint cleaners, wash preservers,shampoos for auto washing, auto-wash and wax products, polishes for trimmetals, protective films for trim metals, plastics cleaners, tarremovers, screen cleaners, engine cleaners, and the like.

Cosmetic products include:

(a) cosmetic skincare products, especially bath products, skin washingand cleansing products, skincare products, eye makeup, lip careproducts, nail care products, intimate care products, foot careproducts;

(b) cosmetic products with specific effects, especially sunscreens,tanning products, de-pigmenting products, deodorants, antiperspirants,hair removers, shaving products, perfumes;

(c) cosmetic dental-care products, especially dental and oral careproducts, tooth care products, cleaners for dental prostheses, adhesivesfor dental prostheses; and

(d) cosmetic hair care products, especially hair shampoos, hair careproducts, hair setting products, hair-shaping products, and haircoloring products.

Textile treatment products include:

Detergents or fabric conditioners, for example, in either liquid orsolid form.

Air fresheners and room fragrancers include:

Products that contain preferably volatile and usually pleasant-smellingcompounds which advantageously can even in very small amounts maskunpleasant odours. Air fresheners for living areas contain, inparticular, natural and synthetic essential oils such as pine needleoils, citrus oil, eucalyptus oil, lavender oil, and the like, in amountsfor example of up to 50% by weight. As aerosols they tend to containsmaller amounts of such essential oils, by way of example less than 5%or less than 2% by weight, but additionally include compounds such asacetaldehyde (in particular, <0.5% by weight), isopropyl alcohol (inparticular, <5% by weight), mineral oil (in particular, <5% by weight),and propellants. Other presentation forms include sticks and blocks.They are produced typically using a gel concentrate comprising essentialoils. It is also possible to add formaldehyde (for preservation) andchlorophyll (preferably <5% by weight), and also further ingredients.Air fresheners are not, however, restricted to living spaces, but mayalso be intended for autos, cupboards, dishwashers, refrigerators orshoes, and even their use in vacuum cleaners is a possibility. In thehousehold (e.g., in cupboards), for example, in addition to the odourimprovers, disinfectants as well are employed, containing preferablycompounds such as calcium phosphate, talc, stearin, and essential oils,these products taking the form, for example, of sachets.

There now follows a series of examples that serve to further illustratethe invention.

EXAMPLE 1 (E/Z)-5,9-dimethyl-9-hydroxy-decen-4-al (I) a)2,6-dimethyloct-7-yne-2,6-diol (2)

The reactor was charged with water (1593 ml) and sulfuric acid (875 g,8.7 mol) was added. The solution was cooled to 20° C.3,7-dimethyloct-6-en-1-yn-3-ol (1, 2.45 kg, 16.1 mol) was added and themixture was stirred at 25° C. for 48 hours.

Water (1.5 l) and methyl tert.-butyl ether (1.6 l) was added and themixture was stirred for 10 minutes. The layers were separated and theaqueous layer was extracted with methyl tert.-butyl ether (1.6 l). Theorganic layers were combined and washed with NaOH 2M (250 ml, pH 0),with saturated KHCO3 solution (700 ml, pH 8-9) and brine (800 ml). Thesolution was dried over MgSO4 and concentrated in vacuo. Residual3,7-dimethyloct-6-en-1-yn-3-ol and volatile side products were removedby distillation over a 20 cm Vigreux column (b.p. 35-104° C. at 0.4mbar). The crude product was wipe-film distilled (150° C. at 0.06 mbar)to afford (2) (1642 g, 69% yield) as a light yellow liquid. The productwill crystallize upon standing. A sample was crystallized from hexane toafford white crystals, m.p. 48-49° C.

1H NMR: 3.36 (s, 1H); 2.40 (s, 1H); 2.20 (s, 1H); 1.67-1.39 (m, 6H);1.43 (s, 3H); 1.16 (s, 6H). 13C NMR: 88.5 (s), 71.7 (d), 71.6, 68.1(2s), 44.2, 44.0 (2t), 30.2, 29.6, 29.5 (3q), 19.8 (t).

MS: 137 (10, M⁺-CH₃, H₂O), 109 (29), 79 (40), 77 (15), 71 (15), 69 (42),66 (59), 59 (100), 56 (28), 43 (91), 41 (21).

b) 2,6-dimethyloct-7-ene-2,6-diol (3)

A reactor equipped with an aeration stirrer was charged with2,6-dimethyloct-7-yne-2,6-diol (2, 2.4 kg, 14.1 mol) and toluene (1.8l). Palladium on activated carbon poisoned with lead (Lindlar catalyst,25 g) was added and the reactor was flushed first with inert gas andthen with hydrogen. The mixture was hydrogenated at 0.1-0.2 bar for 7.5hours until the theoretical amount of hydrogen was consumed. Throughoutthe reaction the temperature was kept at 34-40° C. by means of a waterbath. At the end of the reaction analysis by GC showed 6% overhydrogenated side product. The catalyst was removed by filtration andthe toluene solution of (3) was used for the next synthetic step withoutfurther treatment. A sample of (3) was recrystallized from hexane forspectroscopic analysis, m.p. 46-47° C.

1H NMR: 5.83 (dd, J=17.4, 10.8, 1H); 5.12 (dd, J=17.4, 1.5, 1H); 4.95(dd, J=10.8, 1.5, 1H); 2.29 (bs, 2H); 1.49-1.25 (m, 6H); 1.2 (s, 3H);1.12 (s, 6H). 13C NMR: 145.6 (d), 111.9 (t), 73.6, 71.3 (2s), 44.5, 43.1(2t), 29.6, 28.0 (3q), 19.0 (t).

MS: 154 (1, M⁺-H₂O), 121 (16), 81 (35), 71 (100), 69 (25), 68 (45), 59(36), 56 (36), 55 (18), 43 (53), 41 (17).

c) (E/Z)-5,9-dimethyl-9-hydroxy-decen-4-al (I)

In a pressure vessel with stirrer (Büchi, 5000 ml) a mixture of2,6-dimethyloct-7-ene-2,6-diol in toluene (3, 2.25 l, 7 mol), from theprevious hydrogenation reaction, ethyl vinyl ether (1.26 kg, 17 mol) andphenyl phosphonic acid (13 g, 82 mmol) were added. The autoclave wasflushed and pre-pressurized to 2 bar with nitrogen and heated to 150° C.(pressure 4-6 bar) for 30 minutes. The temperature was then raised to175° C. (pressure 8-10 bar) and maintained for 50 minutes. The reactionmixture was cooled and transferred to a 10 l jacketed reactor. Water (3l) and HCl (2M, 300 ml) was added and the mixture was stirred at 50° C.until GC analysis showed the complete hydrolysis of the acetals of (I)in the mixture. The mixture was neutralized with saturated aqueous KHCO3solution and the layers were separated. The aqueous layer was extractedwith MtBE, the organic layers were combined and washed with acetic acid(10%, 500 ml) dried over MgSO₄ and concentrated in vacuo. The crudeproduct was wipe-film distilled (150° C., 0.06 mbar) to afford (I) (1077g, 78% yield) as a light orange liquid.

The crude material was distilled over a 50 cm, 1′ diameter column withSulzer packing (b.p. 109° C., 0.05 mbar) to afford olfactively pure (I)(514 g, 37% yield). Refractive index

1H NMR; mixture of E/Z isomers: 9.73 (t, J=1.77, 1H); 9.72 (t, J=1.77,1H); 5.07 (t, J=7.07, 2H); 2.46-2.40 (m, 4H); 2.34-2.25 (m, 4H); 2.01(m, 2H); 1.94 (m, 2H); 1.65 (q, J=1.27, 3H); 1.61 (bs, 2H (OH)); 1.59(bs, 3H); 1.48-1.32 (m, 8H); 1.18 (s, 6H); 1.17 (s, 6H). 13C NMR;mixture of E/Z isomers: 203.0, 202.9 (2d), 137.3, 137.2 (2s), 123.2,122.5 (2d), 71.2, 71.1 (2s), 44.5, 44.3, 44.0, 43.7, 40.3, 32.4 (6t),29.6 (4q), 23.6 (q), 23.0, 22.9, 21.2, 21.0 (4t), 16.3 (q).

MS; sum of E/Z isomers: 180 (1, M⁺-H₂O), 96 (33), 93 (27), 81 (82), 69(44), 68 (55), 67 (39), 59 (100), 55 (55), 43 (64), 41 (59).

Odour: floral, green, muguet, hydroxy citronellal aspect

The reported NMR spectra were measured in CDCl₃ at 400 MHz if nototherwise stated; chemical shifts are reported in ppm downfield fromTMS; coupling constants J in Hz. The GC/MS analyses were run using aZB-5 column, if not stated otherwise. All purified products were eithercrystallized and isolated as white solids or purified by distillation invacuo and isolated as colorless oils, the purity was confirmed by GC/MS.Samples for olfactory evaluation were purified by rectification over adistillation column with Sulzer packing.

EXAMPLE 2

In this example, the methodology of Example 27 of GB 981,702 wasfollowed and the product isolated and characterised.

Crystalline hydroxy linalool (171 g, 0.993 mol, m.p. 46-47° C.) wasdissolved in ethyl vinyl ether (240 g, 3.325 mol) and placed in a PARRautoclave. Phosphoric acid (0.6 g) was added and the mixture was heatedat 180° C. for 30 minutes. The mixture was cooled to room temperature,neutralized with triethylamine (2.4 ml) and concentrated in vacuo (100°C., 14 mm). The residue (205.6 g) was added to a mixture of sodiumsulfite (500 g) and water (2000 ml) and stirred for 1 hour. The pH wasset to 7 by adding acetic acid (2 g) and the mixture was then extractedwith MtBE three times. The combined ether extracts were concentrated invacuo to afford the non-aldehydic constituents (90.6 g) In the patentthe inventors reported 44 g of non-aldehydic material. The aqueous layerwas treated with NaOH 30% (1000 ml) while cooling the mixture with anice/water bath. The mixture (pH 14) was then extracted three times withMtBE, the organic layers were combined, washed with sodium bicarbonatesolution and concentrated. The dark viscous residue (91.3 g), in thepatent the inventors reported 182 g, was dissolved in acetone (500 ml)and 10% sulfuric acid (200 ml) was added. The mixture was left standingover night. The mixture was then diluted with water (2000 ml) andextracted five times with MtBE. The combined ether extracts were washedwith sodium bicarbonate and concentrated in vacuo. The crude materialwas purified by distillation (bp. 85° C., 0.5 mbar) to afford a equallydistributed mixture of (E/Z)-5,9-dimethyldeca-4,8-dienal and(E/Z)-5,9-dimethyldeca-4,9-dienal (5.66 g, 3.16% yield). Refractiveindex: n_(D) ²⁰ 1.4682

Odour: Fruity, apple, citrus, fatty, aldehydic, metallic, slightly hotiron, long lasting

1H NMR; mixture isomers: 9.76 (q, J=1.77, 4H); 5.14-5.04 (m, 6H); 4.69(m, 4H); 2.45 (m, 8H); 2.33 (m, 8H); 2.11-1.93 (m, 16H); 1.74-1.66 (m,18H); 1.64-1.59 (m, 12H); 1.57-1.47 (m, 4H). 13C NMR; mixture ofisomers: 202.92, 202.85, 202.83, 202.79 (4d), 146.23, 146.07 (2s),137.41, 137.29, 137.21 (4s), 132.11, 131.83 (2s), 124.47, 124.42,123.21, 123.18, 122.48, 122.40 (6d), 110.27, 110.20 (2t), 44.55, 44.35,44.32, 39.99, 39.54, 37.98, 37.69, 32.29, 31.75, 26.95, 26.80, 26.23,26.19 (14t), 26.07, 26.03, 23.70, 23.69, 22.76 (6q), 21.24, 21.21,21.07, 21.03 (4t), 18.04, 18.00, 16.40, 16.31 (4q).

MS 5,9-dimethyldeca-4,9-dienal; sum of E/Z isomers: 180 (1, M⁺-H₂O), 96(55), 81 (100), 79 (34), 69 (41), 68 (97), 67 (66), 55 (95), 53 (35), 41(95), 39 (37).

MS 5,9-dimethyldeca-4,8-dienal; sum of E/Z isomers: 180 (1, M⁺-H₂O), 137(1), 136 (1), 93 (14), 69 (100), 67 (11), 55 (24), 53 (11), 43 (1), 41(66), 39 (11).

EXAMPLE 3

To a 1000 mL multi-necked flask fitted with stirrer, condenser anddropping funnel is charged a solution of 180 g hydroxylinalool in 180 gtoluene; 0.9 g phosphoric acid (85%); and 0.3 g triethanolamine. Theflask is heated to 125° C. with stirring, and 150 g diethyleneglycoldivinylether is added over 2 hours, and the mixture stirred whilstmaintaining this temperature. After addition, 10 g of toluene is addedto the flask and the mixture is stirred for a further 2.5 hours at thesame temperature. Thereafter, the reaction mixture is washed 3 times at70° C. with a solution of 10 g sodium chloride in 120 g water. Afterwashing with 10% aqueous solution of Sodium bicarbonate and water,toluene is distilled off and the residue fractionated in vacuo to yield(E&Z)-9-hydroxy-5,9-dimethyldec-4-enal as a colorless to pale yellowoil.

EXAMPLE 4

Sodium metabisulphite (9.59 g) was dissolved in water and9-hydroxy-5,9-dimethyldec-4-enal (10 g) was added thereto. Ethanol (10ml) was added to the solution and the mixture became turbid. The mixturewas stirred for 30 minutes at room temperature. GC analysis of theorganic material showed that almost all aldehyde was in the water phasein the form of its sulphonate adduct. The mixture was stirred for afurther 30 minutes before adding 50 ml of MtBE. The layers wereseparated and the aqueous layer was extracted another 2 times with 10 mlMtBE. The pH of the aqueous phase was 4.4. A portion was taken, freezedried and subjected to analysis:

1H NMR (MeOD); mixture of E/Z isomers:

5.19 (t, J=7.09, 2H); 4.25 (m, 2H); 2.32-1.94 (m, 10H); 1.77 (m, 2H);1.71 (s, 3H); 1.65 (s, 3H); 1.46 (m, 8H); 1.18 (s, 12H). 13C NMR (MeOD);mixture of E/Z isomers:

136.0, 135.8 (2s), 124.0, 123.3 (2d), 83.4 (2d), 70.1 (2s), 43.1, 43.0,39.9, 31.7, 31.4 (6t), 27.8 (4q), 23.7, 22.4, 22.3 (4t), 22.2, 14.66(2q). mp>84° C. decomposition.

Thereafter, to the remaining sample, sodium carbonate 15% in water wasadded in portions. An evolution of gas indicated that the sulphonate haddecomposed. The pH was 7.1. More sodium carbonate was added in portionsuntil the mixture reached a pH of 9.45, before the mixture was warmed to40° C. for 30 minutes. The slightly basic aqueous solution was worked upby extraction with MtBE, and the organic phases were combined, washedwith 10% acetic acid, dried and concentrated to yield9-hydroxy-5,9-dimethyldec-4-enal once again.

EXAMPLE 5

INGREDIENT/% Cpd (I) FLOROSA ™ DUPICAL ™ PEONILE ™ PERFUME 80 20COMPOSITION 1 PERFUME 80 19.99 0.01 COMPOSITION 2 PERFUME 80 19.90 0.1COMPOSITION 3

Application in Fine Fragrance

Two fine fragrances, one male-type and one female-type containingcyclohexal were used as comparative formulations.

Both the male-type and the female-type fragrances were modified byremoving cyclohexal and replacing it with equal amounts of the perfumecompositions set forth in the above table to provide three modifiedmale-type fragrances and three modified female-type fragrances.

The modified fragrances and the comparative formulations were eachplaced on a blotter. The odour characteristics of the modifiedfragrances and the comparative formulations were assessed by a panel oftrained perfumers immediately and after 4 hours evaporation.

All modified fragrances were assessed to have remarkably similar odourcharacteristics as the comparative formulations, demonstrating theperfume formulae set forth in the table are suitable as replacers forcyclohexal in a fine perfumery setting.

Application in Fabric Softener

An unperfumed fabric softener base was perfumed with cyclohexal to forma comparative formulation and with similar quantities each of theperfume compositions set forth in the above table to produce testformulations. The perfumed fabric softener compositions were diluted inwater and the odour characteristics of these diluted compositions wereassessed by a panel of trained perfumers.

From the panel assessment it was found that the tests formulationsexhibited remarkably similar odour characteristics to the comparativeformulation, demonstrating the perfume formulae set forth in the tableare suitable as replacers for cyclohexal in a fabric softener setting.

Application in Shower Gel

An unperfumed shower gel base was perfumed with cyclohexal to form acomparative formulation and with similar quantities each of the perfumecompositions set forth in the above table to produce test formulations.The perfumed shower gel compositions were diluted in water and the odourcharacteristics of these diluted compositions were assessed by a panelof trained perfumers.

From the panel assessment it was found that the tests formulationsexhibited remarkably similar odour characteristics to the comparativeformulation, demonstrating the perfume formulae set forth in the tableare suitable as replacers for cyclohexal in a shower gel setting.

Application in Shampoo

An unperfumed shampoo base was perfumed with cyclohexal to form acomparative formulation and with similar quantities each of the perfumecompositions set forth in the above table to produce test formulations.The thus perfumed shampoo compositions were diluted in water and theodour characteristics of these diluted compositions were assessed by apanel of trained perfumers.

From the panel assessment it was found that the tests formulationsexhibited remarkably similar odour characteristics to the comparativeformulation, demonstrating the perfume formulae set forth in the tableare suitable as replacers for cyclohexal in a shampoo setting.

EXAMPLE 6

In the following perfume formulation 5,9-dimethyl-9-hydroxy-decen-4-alor the mixture described in Example 5, and cyclohexal (Lyra)™) areinterchangeable ingredients. 5,9-Dimethyl-9-hydroxy-decen-4-al adds,like cyclohexal, to the body, diffusivity and radiance of the fragrancecomposition.

NIRVANOLIDE 329925-33-9 15.00 DIPROPYLENE GLYCOL 25265-71-8 1 3.96CEPIONATE 24851-98-7 13.00 BENZYL SALICYLATE 118-58-1 10.00 SERENOLIDE477218-42-1 9.00 FLORYMOSS 681433-04-5 9.00 GEORGYWOOD 185429-83-8 7.50ISORALDEINE CETONE ALPHA 1335-46-2 4.50 TROPIONAL 1205-17-0 3.50FLORHYDRAL 125109-85-5 1.00 ISOEUGENOL ACETATE CRYSTAL 93-29-8 0.90CASHMERAN 33704-61-9 0.90 DECALACTONE GAMMA 706-14-9 0.35 PEACH PURE104-67-6 0.30 NEOCASPIRENE EXTRA 89079-92-5 0.25 INDOLENE 50%/CASTOR OIL0.20 AMBROFIX 6790-58-5 0.20 ETHYL VANILLIN 121-32-4 0.15 CYCLAL C68039-49-6 0.14 DAMASCONE ALPHA 24720-09-0 0.09 FILBERTONE 10%/TEC 0.04OXANE 50%/TEC 0.02 5, 9-Dimethyl-9-hydroxy-decen-4-al-- 10.00 100.00

EXAMPLE 7

In the following perfume formulation 5,9-dimethyl-9-hydroxy-decen-4-alor the mixture described in Example 5, and cyclohexal (Lyral™) areinterchangeable ingredients. 5,9-Dimethyl-9-hydroxy-decen-4-al adds,like cyclohexal, to the body, diffusivity and radiance of the fragrancecomposition

AMBROFIX 6790-58-5 0.20 BENZYL SALICYLATE 118-58-1 10.00 CASHMERAN33704-61-9 0.90 CEPIONATE 24851-98-7 13.00 CYCLAL C 68039-49-6 0.14DAMASCONE ALPHA 24720-09-0 0.09 DECALACTONE GAMMA 706-14-9 0.35DIPROPYLENE GLYCOL 25265-71-8 13.96 ETHYL VANILLIN 121-32-4 0.15FILBERTONE 10%/TEC 0.04 FLORHYDRAL 125109-85-5 1.00 FLORYMOSS681433-04-5 9.00 GEORGYWOOD 185429-83-8 7.50 INDOLENE 50%/CASTOR OIL0.20 ISOEUGENOL ACETATE CRYSTAL 93-29-8 0.90 ISORALDEINE CETONE ALPHA1335-46-2 4.50 NEOCASPIRENE EXTRA 89079-92-5 0.25 NIRVANOLIDE329925-33-9 15.00 OXANE 50%/TEC 0.02 PEACH PURE 104-67-6 0.30 SERENOLIDE477218-42-1 9.00 5, 9-Dimethyl-9-hydroxy-decen-4-al-- 10.00 TROPIONAL1205-17-0 3.50 100.00

1. (canceled)
 2. (canceled)
 3. (canceled)
 4. (canceled)
 5. (canceled) 6.(canceled)
 7. (canceled)
 8. (canceled)
 9. (canceled)
 10. (canceled) 11.(canceled)
 12. (canceled)
 13. (canceled)
 14. (canceled)
 15. (canceled)16. (canceled)
 17. (canceled)
 18. A personal care composition, ahousehold care composition or a fine fragrance composition comprisingthe compound 5,9-dimethyl-9-hydroxy-decen-4-al, having the formula (I)


19. A personal care composition, a household care composition or a finefragrance composition compounds according to formula (I) of claim 18,present in an E/Z isomer ratio of from 8:2 to 2:8.
 20. A personal carecomposition, a household care composition or a fine fragrancecomposition according to claim 18 further comprising one or moreadditional compounds selected from the group consisting of:2-cyclohexylidene-2-phenylacetonitrile;4-(octahydro-4,7-methano-5H-inden-5-ylidene)butanal;4-Methyl-2-(2-methyl propyl)tetrahydro-2H-pyran-4-ol; and methyl2-(2-hexyl-3-oxocyclopentyl)acetate.
 21. A personal care composition, ahousehold care composition or a fine fragrance composition according toclaim 20 wherein 2-cyclohexylidene-2-phenylacetonitrile is present in0.001 to 10 parts by weight per 1 part by weight5,9-dimethyl-9-hydroxy-decen-4-al.
 22. A personal care composition, ahousehold care composition or a fine fragrance composition according toclaim 20 wherein 4-methyl-2-(2-methylpropyl)tetrahydro-2H-pyran-4-ol isemployed in 0.001 to 20 parts by weight per 1 part by weight5,9-dimethyl-9-hydroxy-decen-4-al.
 23. A personal care composition, ahousehold care composition or a fine fragrance composition according toclaim 20 wherein 4-(octahydro-4,7-methano-5H-inden-5-ylidene)butanal, isemployed in 0.0001 to 0.5 parts by weight per 1 part by weight5,9-dimethyl-9-hydroxy-decen-4-al.
 24. A personal care composition, ahousehold care composition or a fine fragrance composition according toclaim 20 wherein the 5,9-dimethyl-9-hydroxy-decen-4-al compound ispresent in said perfume composition in an amount of 1 to 30% by weightbased on the total weight of any of the said personal care composition,a household care composition or a fine fragrance composition.
 25. Apersonal care composition, a household care composition or a finefragrance composition according to claim 18, further comprising at leastone perfume ingredient
 26. A personal care composition, a household carecomposition or a fine fragrance composition according to claim 25,wherein said at least one perfume ingredient is not cyclohexal.
 27. Aprocess of forming a personal care composition, a household carecomposition or a fine fragrance composition, said process comprising thesteps of: I) reaching hydroxylinalool with ethyl vinyl ether in acidunder an inert gas atmosphere at 1 to 100 bar, and a temperature of (−)10 to 200 degrees centigrade, to form a reaction mixture comprisingacetals; II) acidifying the cooled reaction mixture at (−20) to 40degrees centigrade and atmospheric pressure to hydrolyse said acetals;III) neutralising the reaction mixture in a base before adjusting the pHof the reaction mixture to a slightly acidic pH of 2 to7, to yield5,9-dimethyl-9-hydroxy-decen-4-al (I); and optionally IV) distilling thereaction mixture to isolate 5,9-dimethyl-9-hydroxy-decen-4-al; and, V)incorporating the isolated 5,9-dimethyl-9-hydroxy-decen-4-al within thepersonal care composition, or the household care composition or the finefragrance composition.
 28. A personal care composition, a household carecomposition or a fine fragrance composition comprising a compoundaccording to formula (I) of claim 18, wherein the said composition isfree of cyclohexal.
 29. A personal care composition, a household carecomposition or a fine fragrance composition according to claim 20wherein methyl 2-(2-hexyl-3-oxocyclopentyl)acetate is present in anamount of 0.001 to 10 parts by weight per 1 part by weight of5,9-dimethyl-9-hydroxy-decen-4-al.
 30. A personal care composition, ahousehold care composition or a fine fragrance composition comprisingcompounds according to claim 19, wherein the said personal carecomposition, a household care composition or a fine fragrancecomposition is free of cyclohexal.
 31. A personal care composition, ahousehold care composition or a fine fragrance composition according toclaim 18, further comprising at least one adjuvant.
 32. A personal carecomposition, a household care composition or a fine fragrancecomposition according to claim 31, wherein the at least one adjuvant isan anti-oxidant.
 33. A personal care composition, a household carecomposition or a fine fragrance composition according to claim 19,further comprising at least one adjuvant.
 34. A personal carecomposition, a household care composition or a fine fragrancecomposition according to claim 33, wherein the at least one adjuvant isan anti-oxidant.
 35. A method of imparting a muget odor note to apersonal care composition, a household care composition or a finefragrance composition, the method comprising the step of: adding to orincluding within the personal care composition, a household carecomposition or a fine fragrance composition a compound according toformula (I) of claim
 18. 36. A method of imparting a muget odor note toa personal care composition, a household care composition or a finefragrance composition, the method comprising the step of: adding to orincluding within the personal care composition, a household carecomposition or a fine fragrance composition compounds according to claim19.